Disazo pigments



Patented June 27, 1967 1-amino-2-bromo-4-cyananthraquinone,

3,328,335 Z-aminoanthraquinone,

DISAZO PIGMENTS Hansrolf Loeticl, Neu-Allschwil, and Willy Mueller, z amino'3'chloranthraquinone Riehen, Switzerland, assignors to Ciba Limited, Basel, u Switzerland, :1 company of Switzerland 5 zamln'oli3dlchloranthl'aqulnone, N0 Drawing. Filed Oct. 13, 1963, Ser. No. 317,125 2-am1r103-methoxyanthraquinone, an Claims priority, application Switzerland, Oct. 23, 1962, S-amino-l:9-isothiazole-anthrone.

12,402/ 62 6 Claims (Cl. 260 174) The following coupling components may be particularly mentioned: 7 The present invention provides valuable new disazo 10 pigments of the formula 2-hydroxy-3-naphthoic acid,

6-brorno-2-hydroxy-3-naphthoic acid, and 6-methoxy-2-hydroxy-3-naphthoic acid.

NHCOBN=NA in which A represents an anthraquinone radical, B represents the radical of a coupling component, which radical contains a hydroxyl group or an enolizable keto group in ortho position to the azo group, and R represents the radical of a diamine.

In the Formula 1 above, A advantageously represents the radical of an a-aminoanthraquinone and R an arylene radical. Of special interest are dyestuffs of the formula The azo dyestufi carboxylic acids thus obtained are Also suitable are:

2-hydroxycarbazole-3-carboxylic acid,

2-hydroxydiphenyleneoxide-3-carboxylic acid,

2-hydroxyanthracene-3 carboxylic acid,

l-(meta' or para-carb'oxyphenyl)-3-methyl-5-pyrazolone,

acetoacetic acid ethyl ester, v

3 and 4-acetoacetylaminobenzene carboxylic acid.

O N=N N: I O

I I! O O in which R has the meaning given above, and Y repretreated with agents that are capable of converting carsents a hydrogen atom or a halogen atom or an alkoxy boXylic acids into their acid halides, for example, their group. acid chlorides or bromides, particularly with phosphorus The new dyestufis are obtained when two mols of a halides such as phosphorus pentabromide or phosphorus carboxylic acid halide free from acidic groups imparttrichloride or phosphorus pentachloride, phosphorus oxying solubility in water, especially sulfonic acid or car- 40 halides and advantageously with thionly chloride. boxylic acid groups, that corresponds to the formula The treatment with acid halogenating agent of the i kind defined is advantageously carried out in an inert (3) A N'. N BCOHa1 organic solvent such as dimethylformamide, .a chloroin Which A and B have the meanings giv n a v are benzene, for example, monochlorbenzene or dichlorocondensed With a diamine fr e fr acidic gr p benzene, toluene, Xylene or nitrobenzene; in the case of parting solubility in Water. the five last-mentioned solvents, the treatment may be The carboxylic acids from which the azo dyestuff carcarried out with the addition of dimethylformamide. boxylic acid halides of the Formula 3 are deriv d ar In the preparation of the carboxylic acid halides it is advantageously Obtained y p g a diazotized aminogenerally of advantage first to dry the azo compounds anlhraqulnone, especially an u-amlnoalllllfaqlllflone, With that have been prepared in aqueous medium or to free a PheHOlic an enollc coupling mponent containing a them from water by azeotropic distillation in an organic carboxylie acid gI HP r a CaIbOXYliC acid ester g p, it solvent. If desired, this azeotropic drying can be carried being necessary in the latter case to hydrolyse the ester out immediately rior to th treatment with the acid group. The following aminoanthraquinones may be menhalogenating agents. tioned: In accordance With the process of the invention, the

monocarboxylic acid halides so obtained are condensed in a molar ratio of 2:1 with diamines, especially aromatic diamines, advantageously those of the benzene or diphenyl series. As diamines of the benzene series there may be mentioned more especially those of the formula l-aminoanthraquinone,

1-amino-2-chloranthraquinone, 1-amino-2-bromanthraquinone, 1-amino-3-chloranthraquinone,

1-amino-6- or 7-chloranthraquinone, V

l-amino-S 8-dichloranthraquinone, X

1-amino-Swhloranthraquihone, t 1-amino-3-bromanthraquinone, H

1-amino-2 4-dibromanthraquinone, 1-amino-2-rnethylanthraquinone, X 1 1.. i 3 fl th i in which X represents a hydrogen or a halogen atom or a 1-amino-4-, 5- or 6-methoxyanthraquinone, low'moleculal' alkyl or f y f pi 3 t ifi th l th i As examples the following amines may be mentioned: 1-amino-4- or S-benzoylaminoanthraquinone, ethylenediamine,

1-amino-4-cyananthraquinone, l :4-diaminobenzene,

1-amino-3-cyananthraquinone, 1 :3-diaminobenzene,

, 1-amino-4-nitroanthraquinone, 1 3-diamino-4-methylbenzene,

z3Idl?m1lm'2l6'dlmethy1benzene hour, and the whole stirred for 1 hour at 20 to 25 C. The f l f l sulfuric acid solution was then cautiously poured on to i 'dlchloro'A'A 'dlammodlphenyl 350 parts of ice, when the diazonium sulfate precipitated I in the form of a yellow suspension.

The solution of coupling component was prepared as 3 -dimethyl-4 4'-diaminodiphenyl, 3 '-dimethoxy-4 4'-diaminodiphenyl, 20 3 :5 S '-tetrach1oro-4 4'-diaminodiphenyl,

3 4 1:3-diamino-4-methoxybenzene, In contrast with comparable dyestuffs described in 1:3-diamino-4:6-dichlorobenzene, United States specification No. 2,273,116, the dyestuffs 1:3-diamino-4-chlorobenzene, obtained by the process of the invention are distinguished l:3-diamino-2:S-dichlorobenzeue, by a substantially better fastness to migration. 1:4-diamino-2-chlorobenzene, 5 The following examples illustrate the invention..Un- 1:4-diamino-2-bromobenzene, less otherwise stated, the parts and percentages are by 1 :4-diamino-2-cyanobenzene, Weight. 1:4-diamino-2:S-dichlorobenzene, Example 1 124'diamlno'zmelhylbenzene 130 parts of sulfuric acid monohydrate were cooled to 1i4'dlamlno'zzs'dlmethylbenzene C. and 7.1 parts of sodium nitrite vwere introduced in iji'gl l 'g' fi g small portions with rapid stirring. The nitrosyl sulfuric l i oxy enzene acid was then heated to 70 C. in the course of 40 minutes, l l l maintained at that temperature for 30 minutes and then 1 4'dlamlnO'2:s'dlethoxybenzene cooled to room temperature. 25.75 parts of 1-amino-3- iz3'd1a'mmo'4:6'dlmethylbenzene chloranthraquinone were then added in the course of 1 4 3 3 3 3 3 follows:

:5 'dlmethylAA 'dlammodlphenyl 19.1 parts of 2:3-hydroxynaphthoic acid were dissolved 2"s'dlzlmlrlochrysene in 400 parts of a 1:1 mixture of alcohol and water and 4:11'd1am1mfluqranthene parts of aqueous 30% sodium hydroxide solution. After F 1:5'd1amlnnaPhtha1ene filtering until clear, 30 parts of sodium acetate were added dlantmolienzenthlazole 511.611 as and the pH value adjusted to 6 with acetic acid.

'ammophenyl)'6'ammobenzthlazole' The solution was cooled to 10 C. and then the di- The condensation between the carboxylic acid halides azonium sulfate was allowed to run in (pH 4 to 6) with of the kind defined above and the amines is advantasimultaneous dropwise addition of concentrated sodium geously carried out in an anhydrous medium. Under these 30 hydroxide solution. After the coupling, the reaction mixconditions it generally proceeds surprisingly easily even ture was heated to 70 C., filtered and the filter residue at temperature within theboiling range of the common orwashed free from salt. 190 parts of moist filter residue ganic solvents, for example, toluene, monochlorobenzene, were obtained. dichlorobenzene, trichlorobenzene, nitrobenzene and the The press cake was feed from water azeotropically in like. (In order to accelerate the reaction it is generally 650 parts of ortho-dichlorobenzene by heating to an inof advantage to use an agent capable of binding acid, for ternal temperature of 150 C. (with the use of a descendexample, anhydrous sodium acetate or pyridine.) Some ing condenser). After cooling to 90 C., one part of diof the dyestuffs obtained are in the form of crystals and methylformamide and 24 parts of thionyl chloride were some are amorphous,'and most of them are obtained in 40 added dropwise, and the whole stirred for 2 hours at a good yield and in a pure state. It is advantageously 100 to 1 10 C. The reaction mixture was allowed to cool first of all to separate the acid chlorides prepared from the to 20 C., filtered, the filter residue Washed with 520 carboxylic acids. In some cases, however, separation of the parts of dichlorobenzene and 400 parts of benzene, and acid chlorides can be dispensed with without harm, and the acid chloride dried in vacuo at C.; yield: 43.35 the condensation carried out immediately subsequent to parts. the preparation of the carboxylic acid chlorides. 4 4.75 parts of the acid chloride were introduced into The new dyestuffs are valuable pigments that can be 350 parts of dichlorobenzene at room temperature. 0.885 used for a very wide variety of purposes. For example, part of 2:5-dichloro-1:4-phenylenediamine, dissolved in they can be used in a finely divided form for the spin dye- 130 parts of dichlorobenzene, were then added. The ing of rayon and viscose, cellulose ethers, cellulose esters, whole was heated to 'C., the temperature raised to polyamides, polyurethanes and polyesters; for the manu- 50 140 C. in the course of 8 hours, and the reaction mixfacture of colored lacquers or as lake-formers; and for ture stirred for a further 8 hours at 140 C. The pigment coloring solutions and products made of cellulose acethus formed was isolated by filtration at 100 C. and then tate, nitrocellulose, natural or synthetic resins such as washed with 320 parts of hot dichlorobenzene, 160 parts polymerization or condensation resins, for example, of methanol and 200 parts of water. 4.85 parts of the aminoplasts, alkyld resins, phenoplasts, polyolefines such 55 dyestuff of the formula on (31 OH N|=N CONH NHOC N= -N o I ll 01 l) l as polystyrene, polyvinylchloride, polyethylene, polyprowere obtained which, when incorporated in polyvinylpylene, polyacrylonitrile, rubber, caseine, silicone and chloride on a roller mill, gave a yellowish red tint possilicone resins. They can also be used with advantage in sessing a very good fastness to light and to migration. the manufacture of colored pencils, cosmetic preparations In the following table are listed further components and laminated sheet material. which yield pigment dyestuffs by diazotizing the diazo In contrast with the nearest comparable dyestuffs decomponents listed in column 1, coupling with 2-hydroxyscribed in German patent specification No. 921,223 which 3-naphthoic acid, preparation of the acid chloride of differ from the dyestuffs of the invention in that they conthe azo dyestuif carboxylic acid thus obtained and contain a benzene radical instead of an anthraquinone radidensing the latter in a molar ratio of 2:1 with the dical, the dyestuffs of the invention are distinguished by a amines listed in column 11. Column III indicates the tints substantially better fastness to light. obtained with the pigments in a polyvinyl chloride film.

I II III Lamina-3 chloranthraquinone Dichloro-paraphenylene-diamine Yellowish red.

Monochloro-paraphenylenediamine.. Red. Chloro-methylparaaphefiylenediamiu Red. Chloro-rnethoxy-para-phenylenediamin Red. Dichlorobenzidine Red. Dimethyl-para-phenylenediamine. Bluish Red. Dimethylbenzidine Do.

8 Para-phenylenediamine Do.

9 Banridinp D0,

10 Dichloro-para-phenylenediamine Red.

11 do Bemid Bluish red 12--- l-amino-Z-bromanthraquinone Dichlorobenzidiue Do.

13 l-amino-8-chloranthraquinoue Dichloro-para phenyleuediamine Red.

14-" Q-aminoanthraquinone do Yellowish red.

15--- 2-amino-3-chloranthraquinone Red.

17--- 2-amino-1:3-dichlor0anthraquinone- Do.

18-.. 2-amino-3-bromo-anthraquinone Para-phenylenediamine- Do.

19 o Dichloro-para phenylenediamine Red.

10 l-amino-Zz4-dibromoanthraquinone Dichlorobenzidine Brown.

21 0 Dichloro-para-phenylenediamine Do.

22.-- 1-a .mino-3-trifluoromethylanthraquinone. do Red.

The l-amino-3-trifiuoromethylanthraquinone could be prepared as follows:

1-amino-2-methyl-4-bromanthraquinone was converted into 1-bromo-3-methylanthraquinone (M.P. 204 to 205 C.) -by diazotizing and boiling the diazonium salt in alcohol, l-chloro 3 -trichloromethylanthraquinone (M.P. 155.5 to 156.5 C.) was obtained therefrom by chlorinaazo dyestutf carboxylic acid chloride were obtained after drying.

2.55 parts of the acid chloride thus obtained were introduced into 130 parts of dichlorobenzene and then condensed with 0447 part of 2:5-dichloro-1:4-phenylenediamine dissolved in 90 parts of dichlorobenzene in a manner analogous to that described in Example 1.

Example 2 As described in Example 1, 13.38 parts of 1-amino-3- chloranthraquinone were diazotized in 75 parts of monohydrate and 4 parts of sodium nitrite and then cautiously pouredon to 250 parts of ice.

11.38 partsof 3-methyl 1 phenyl-(3'-carboxy-)-5- pyrazolone were dissolved in 260 parts of a 1:1 mixture of alcohol and water and 10 parts of sodium hydroxide solution. After filtering until clear, 20 parts of .sodium acetate were added and the pH value adjusted to 6 with acetic acid.

scribed in Example 1. After cooling to 90 C., 1 part of i dimethylformamide, 12 parts of thionyl chloride and a further 130 parts of dichlorobenzene were added dropwise. The whole was stirred for 2 hours at 100 C.,

whereupon the reaction mixture was cooled to 20 C.,

The reaction mixture was filtered, and the filter residue washed with 160 parts of hot dichlorobenzene, parts of methanol and parts of water; yield: 2.4 parts of the dyestutf of the formula When worked into polyvinyl chloride on a roller mill, it

yielded yellow tints possessing a very good -fastness to migration and a good fastness to light.

A reddish yellow was obtained by using benzidine instead of 2 S-dichloro-l 4-phenylenediamine.

Exampl e 3 25.7 parts of l-amino-3-chloranthraquin0ne and 30 parts of 30% hydrochloric acid were stirred for several hours in parts of 100% acetic acid, the suspension cooled to 0 to 5 C., and then diazotized at 0 to 5 C. by

.the dropwise addition of 6.9 parts of sodium nitrite dissolved in 20 parts of water. A clear, yellow diaz'o solution was obtained. This solution was then run into a solution of 15 parts of acetoacetic acid methyl ester and 30 parts of crystalline sodium acetate in 600 parts of water at 30 to 35 C. Coupling was instantaneous. The reaction mixture was stirred for 1 hour at 30 to 35 C., filtered, and the filter residue washed with cold water until as free from salt as possible.

The moist press-cake was then stirred in 600 parts of methanol, and 50 parts by volume of 30% sodium hydroxide solution were aded. The mixture was stirred for 1 hour at 55 to 58 C., during which process the sodium salt of the azo dyestutf carboxylic acid separated out in the form of a yellow-olive precipitate. After hydrolysis, the reaction mixture was rendered acid to congo paper at 75 C. with 75 parts of concentrated hydrochloric acid, filtered, the filter residue washed free from salt with water 7 8 and then dried. 28 parts of an azo dyestuff carboxylic acid and filtered. The filter residue was washed successively of the formula with 300 parts of dichlorobenzene at 130 C. and 150 O N=NCH-COOH parts of cold methanol. Finally, it was washed with hot H Water and then dried in vacuo at 95 to 100 C. About 4 1 5 parts of a soft, yellow pigment powder were obtained that colored synthetic materials and lacquers pure, greenish 01 yellow tints possessing a very good fastness to migration, 1 to overstripe bleeding and to light it corresponded to the 0 formula were obtalned.

(I) N=NC "C OHN NHOOCHN=N O OH; I I II I 00 Cl Cl I OH; l) 01 37.08 parts of the azo dyestuff carboxylic acid were By replacing, in the above example, 2:5-dichloro-1:4- stirred in 350 parts of ortho-dichlorobenzene, 0.2 .part of phenylenediamine with 2-chloro-5-methyll:4-phenylene dimethylfonnamide was added and then 12 parts of thionyl diamine, a neutral yellow having the same good properchloride were added dropwise at 95 to 100 C. Stirring ties was obtained. When it was rep With benlidifl was continued until the chlorination was complete, that or. 2:5-dimethyl-1:4-phenylenediamine, a reddish yellow is to say, for about 1 hour at 100 to 110 C. When the and an orange were obtained respectively, both tints exclear, yellow solution cooled, the azo dyestutf carboxylic hibiting the same good properties as when 2:5-dicl1loroacid chloride precipitatedin the form of handsome golden- 1:5-phcnylened1amine was used. yellow needles. The vproduct was isolated by suction filtra- What we claim is: tion, washed with benzene and then dried in vacuo at 1. A disazo pigment of the formula O N: N=N H I I I I H H0 CONHRNHCO 0H I II o to C.: melting point 233 C. The azo dyestufi carin which X is a member selected from the group consistboxylic acid chloride corresponded to the formula ing of chlorine, bromine and trifluoromethyl, Y'is a member selected from the group consisting of hydrogen, 0 bromine and lower alkoxy, R is a member selected from II I I the group consisting of phenylene and diphenylene radicals either unsubstituted or substituted by chlorine, lower GHQ 5 lower alkyl and lower alkoxy groups. 2. A disazo pigment of the formula shown in claim 1 H in which Ris a radical of the formula 0 X1 3.9 parts of the acid chloride thus obtained were stirrred O in 150 parts of ortho-dichlorobenzene and dissolved at I to C. 0.9 part of 2:5-dichloro-1:4-phenylenedi- X1 amine dissolved in 30 parts of ortho-dichlorobenzene was in which X represents a member selected from the group added and condensation carried out for 8 hours at 75 Consisting of hydrogen, chlorine, lower alkyl and lower to C. The reaction mixture was cooled to 100 C. alkoxy.

8,328,385 9 1O 3. The dyestuff of the formula 4. The dy estuff of the formula 01 Cl (I)H on 01 11 I CONH=NHOC --N=N 0 II o 5. The dyestuff of the formula H0 01 OH o N=N CONHQNHOCA$NN CO0 I 6. The dyestulf of the formula OH 01 OH 1TI=N CONHQNHOC N N o CF; F30 v ll References Cited UNITED STATES PATENTS 1,992,917 2/ 19'35 Kirst et al 260-160 X CHARLES B. PARKER, Primary Examiner. DONALD M. PAPUGA, Assistant Examiner. 

1. A DISAZO PIGMENT OF THE FORMULA 